The β-fragmentation of 2,2-difluoro-saccharide anomeric alkoxyl radicals, generated under oxidative condition by treatment of the respective alcohols with (diacetoxyiodo)benzene (DIB) and iodine, afforded 1,1-difluoro-1-iodo alditols in high yield. The reactivity of the fluorinated radical generated by rupture of the C−I bond has been preliminarily assessed by reductive deiodination with tributyltin hydride/AIBN and intermolecular allylation using the Keck reaction.